JP2582792B2 - Titanocenes, their preparation and compositions containing them - Google Patents
Titanocenes, their preparation and compositions containing themInfo
- Publication number
- JP2582792B2 JP2582792B2 JP62191529A JP19152987A JP2582792B2 JP 2582792 B2 JP2582792 B2 JP 2582792B2 JP 62191529 A JP62191529 A JP 62191529A JP 19152987 A JP19152987 A JP 19152987A JP 2582792 B2 JP2582792 B2 JP 2582792B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- titanocene
- group
- alkyl group
- aromatic ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title description 52
- 238000002360 preparation method Methods 0.000 title description 3
- -1 Cyclopropyl Chemical group 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 125000002837 carbocyclic group Chemical group 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 claims 10
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 claims 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims 1
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical group OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 description 17
- 239000002904 solvent Substances 0.000 description 14
- JAGHDVYKBYUAFD-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C1C=CC=[C-]1.C1C=CC=[C-]1 JAGHDVYKBYUAFD-UHFFFAOYSA-L 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 229920005862 polyol Polymers 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 9
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 6
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000600 sorbitol Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 206010034972 Photosensitivity reaction Diseases 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000036211 photosensitivity Effects 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- 125000001999 4-Methoxybenzoyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C(*)=O 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- NCGDZSKXOVPIBG-UHFFFAOYSA-N C(CCC)CCCCCC.[Li] Chemical compound C(CCC)CCCCCC.[Li] NCGDZSKXOVPIBG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 238000004587 chromatography analysis Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- LSCGCIBAIZLHPL-UHFFFAOYSA-N (2,2,4,5,5-pentamethyl-1,3-dioxolan-4-yl)-phenylmethanone Chemical compound O1C(C)(C)OC(C)(C)C1(C)C(=O)C1=CC=CC=C1 LSCGCIBAIZLHPL-UHFFFAOYSA-N 0.000 description 1
- FBVNHBVWPOQANP-UHFFFAOYSA-N (4-methoxyphenyl)-(2,2,4-trimethyl-1,3-dioxolan-4-yl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1(C)OC(C)(C)OC1 FBVNHBVWPOQANP-UHFFFAOYSA-N 0.000 description 1
- HYRXKONWUWXETA-UHFFFAOYSA-N (4-methylphenyl)-(2,2,4-trimethyl-1,3-dioxolan-4-yl)methanone Chemical compound C1=CC(C)=CC=C1C(=O)C1(C)OC(C)(C)OC1 HYRXKONWUWXETA-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- GGGLSFGLBRHLLH-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)-2-hydroxy-2-methylpropan-1-one Chemical compound CC1=CC=C(C(=O)C(C)(C)O)C(C)=C1 GGGLSFGLBRHLLH-UHFFFAOYSA-N 0.000 description 1
- MLKIVXXYTZKNMI-UHFFFAOYSA-N 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one Chemical compound CCCCCCCCCCCCC1=CC=C(C(=O)C(C)(C)O)C=C1 MLKIVXXYTZKNMI-UHFFFAOYSA-N 0.000 description 1
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- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZKQFHRVKCYFVCN-UHFFFAOYSA-N ethoxyethane;hexane Chemical compound CCOCC.CCCCCC ZKQFHRVKCYFVCN-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004407 fluoroaryl group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- YQCFXPARMSSRRK-UHFFFAOYSA-N n-[6-(prop-2-enoylamino)hexyl]prop-2-enamide Chemical compound C=CC(=O)NCCCCCCNC(=O)C=C YQCFXPARMSSRRK-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- LMAZKPOSWVOFGY-FBAUPLQOSA-N orine Natural products CO[C@H]1C[C@H](O[C@H]2CC[C@]3(C)[C@H]4C[C@@H](OC(=O)C=Cc5ccccc5)[C@]6(C)[C@@](O)(CC[C@]6(O)[C@]4(O)CC=C3C2)[C@H](C)OC(=O)C=Cc7ccccc7)O[C@H](C)[C@H]1O LMAZKPOSWVOFGY-FBAUPLQOSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- GLPANIVUIAGBPX-UHFFFAOYSA-N phenyl-(2,2,4-trimethyl-1,3-dioxolan-4-yl)methanone Chemical group O1C(C)(C)OCC1(C)C(=O)C1=CC=CC=C1 GLPANIVUIAGBPX-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 229920001603 poly (alkyl acrylates) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical compound NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/28—Titanium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/12—Nitrogen compound containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/122—Sulfur compound containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/124—Carbonyl compound containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/126—Halogen compound containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/148—Light sensitive titanium compound containing
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、弗素化芳香族基を含むチタノセン、このよ
うなチタノセンの製造方法およびこのようなチタノセン
からなるエチレン性不飽和化合物の放射線重合のための
開始剤に関するものである。The present invention relates to titanocenes containing fluorinated aromatic groups, a process for the preparation of such titanocenes and the radiation polymerization of ethylenically unsaturated compounds comprising such titanocenes. For initiators for
ヨーロツパ特許A−O,122,223で、フルオロアリール
配位子を持つチタノセンがすぐれた光重合開始剤である
ことが公知である。この種のチタノセンは結晶性であ
り、これらは取扱い上にいくつかの困難がある。このよ
うなチタノセンによつて達成することのできる感光度は
感光性組成物中へのそれらの可溶性によつて影響を受け
る。It is known from European Patent A-0,122,223 that titanocenes with fluoroaryl ligands are excellent photoinitiators. This type of titanocene is crystalline and they have some difficulties in handling. The photosensitivity achievable with such titanocenes is affected by their solubility in the photosensitive composition.
本発明は、式(I) [式中、2つのR1基は各々独立して、非置換またはC1〜
C18−アルキル基で1置換または多置換されたシクロペ
ンタジエニル であり、R2は、金属−炭素結合に対して
の2つのオルト位の少なくとも一方が弗素で置換されて
いる6員の炭素環の芳香族環であって、芳香族環はさら
に置換基を含有してもよく、R3はR2と同一の意味を有
し、R2は少なくとも1個の式−(CzH2zO)0−R9(式
中、zは2−6の数、0は1−20の数でR9はHまたはC1
−C18−アルキルである)の基を含有し、この基は芳香
族環に直接または式−O−で表わされる架橋基を介して
結合されていてもよい。] で示されるチタノセンに関するものである。 The present invention relates to a compound of the formula (I)[Where the two R1The groups are each independently unsubstituted or C1~
C18-Cyclopropyl mono- or polysubstituted with alkyl groups
Ntadienyl And RTwoIs relative to the metal-carbon bond
At least one of the two ortho positions is replaced by fluorine
A six-membered carbocyclic aromatic ring, wherein the aromatic ring is
May contain a substituent, RThreeIs RTwoHas the same meaning as
Then RTwoIs at least one of the formulas-(CzHTwozO)0−R9(formula
Where z is the number of 2-6,0Is the number of 1-20 and R9Is H or C1
−C18-Alkyl), which is aromatic
Directly to the aromatic ring or via a bridging group of the formula -O-
They may be combined. ] It relates to titanocene shown by these.
R1基は好ましくは同一の基である。R1に対する置換基
として可能な基は、1〜18個、好ましくは1〜12個、特
に好ましくは1〜6個の炭素原子の直鎖または枝分れア
ルキル、例えばメチル、エチル、プロピル、イソプロピ
ル、n−ブチル、t−ブチル、ペンチル、ヘキシル、オ
クチル、デシル、ドデシル、テトラデシル、ヘキサデシ
ル、オクタゼシルである。The R 1 groups are preferably the same groups. Possible groups as substituents for R 1 are straight-chain or branched alkyl of 1 to 18, preferably 1 to 12, particularly preferably 1 to 6, carbon atoms, such as methyl, ethyl, propyl, isopropyl , N-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octazecil.
R1の基は、3個以下の、特に1個の置換基を含有する
ことができる。特に2つの基R1がシクロペンタジエニル
またはメチルシクロペンタジエニル 基である。 R1Contains no more than 3, especially one substituent
be able to. Especially two groups R1Is cyclopentadienyl
Or methylcyclopentadienyl Group.
6員の炭素環芳香族の、しかも弗素置換された環基の
R2は、例えば弗素置換されたインデン、インダン、フル
オレン、ナフタレンであり、特にフエニルである。好ま
しくは、2つのオルト位が弗素で置換されたものがよ
い。R2基は少なくとも1個の式−(CzH2zO)0−R9(式
中、zは2〜6の数、0は1〜20の数、R9はC1〜C18−
アルキルである)のポリオキサアルキレンを含有するも
のであり、この基は芳香族環に直接結合されているか、
式−0−で表わされる架橋基を介して結合されていても
よい。R2はさらに例えばアルキル、シクロアルキル、ア
リール、アラルキル、ヒドロキシル、アルコキシ、カル
ボキシル、アルコキシカルボニル、ハロゲン、またはシ
アノのような環置換基を含有していてもよい。これらの
例としては、好ましくは1〜18個の特に好ましくは1〜
6個の炭素原子を持つもの例えば、メチル、エチル、プ
ロピル、ブチル、ペンチル、ヘキシルおよびこれらの対
応アルコキシ基であり、特に、好ましいのはメチルおよ
びメトキシであり;好ましくは5または6個の環炭素原
子をもつたシクロアルキル、好ましくは6〜16個の炭素
原子のアリールおよび好ましくは7〜16個の炭素原子の
アラルキル、例えば、シクロペンチル、シクロヘキシ
ル、フエニルまたはベンジルであり;ヒドロキシ、カル
ボキシル、CN、例えばF、ClまたはBrのようなハロゲ
ン、およびメチルクロライド、ブロマイドまたはアイオ
ダイドのようなアルキルハライドで4級化することので
きる第3級アミノである。アミノの例としては、ジメチ
ルアミノ、ピロリジル、ピペリジル、ピペラジル、モル
ホリルおよびN−メチルピペラジルであり;アルコキシ
基中に好ましくは1〜18個の、特に好ましくは1〜6個
の炭素原子を持つアミノアルコキシカルボニル、アミノ
基中に1〜12個の炭素原子を持つ1個または2個のアル
キル基を持つアミノカルボニルまたは複素環アミンを含
むアミノカルボニル、例えばピロリジン、ピペリジン、
ピペラジン、N−メチルピペラジンおよびモルホリンで
あり;またアルキルハライドで4級化することのでき
る、好ましくは1〜6個の炭素原子を持つアルキルを含
む第3アミノアルキルがある。6-membered carbocyclic aromatic and fluorine-substituted ring group
R 2 is, for example, fluorine-substituted indene, indane, fluorene, naphthalene, especially phenyl. Preferably, two ortho positions are substituted with fluorine. R 2 groups are at least one of the formula - (CzH 2 zO) 0 -R 9 ( wherein, z is a number of 2 to 6, 0 is the number of 1 to 20, R 9 is C 1 -C 18 -
Which is an alkyl) which is directly attached to the aromatic ring,
It may be bonded via a crosslinking group represented by the formula -0-. R 2 may further contain a ring substituent such as, for example, alkyl, cycloalkyl, aryl, aralkyl, hydroxyl, alkoxy, carboxyl, alkoxycarbonyl, halogen, or cyano. Examples of these are preferably 1 to 18, particularly preferably 1 to 18.
Those having 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl and their corresponding alkoxy groups, especially preferred are methyl and methoxy; preferably 5 or 6 ring carbons A cycloalkyl having an atom, preferably an aryl of 6 to 16 carbon atoms and an aralkyl of preferably 7 to 16 carbon atoms, for example cyclopentyl, cyclohexyl, phenyl or benzyl; hydroxy, carboxyl, CN, for example Tertiary aminos that can be quaternized with halogens such as F, Cl or Br, and alkyl halides such as methyl chloride, bromide or iodide. Examples of amino are dimethylamino, pyrrolidyl, piperidyl, piperazyl, morpholyl and N-methylpiperazyl; aminoalkoxycarbonyl having preferably 1 to 18, particularly preferably 1 to 6, carbon atoms in the alkoxy group Aminocarbonyls, including aminocarbonyl or heterocyclic amines having one or two alkyl groups having from 1 to 12 carbon atoms in the amino group, such as pyrrolidine, piperidine,
Piperazine, N-methylpiperazine and morpholine; also tertiary aminoalkyls which can be quaternized with alkyl halides, preferably containing alkyls having 1 to 6 carbon atoms.
R3はR2と同一の意味を有する。R 3 has the same meaning as R 2 .
好ましい具体例において、R2およびR3は、2,6−ジフ
ルオロフエン−1−イルであつて、これに1種以上の遊
離の、またはエーテル化ポリオキサアルキレン基が直接
または式−O−で表わされる架橋基を介して結合してい
るものであり、このものはさらに1種または2種の同一
または異なる置換基を含有しているものであつてもよ
い。In a preferred embodiment, R 2 and R 3 are 2,6 shall apply difluoro full en-1-yl, of one or more free thereto, or directly or by the formula -O- etherified polyoxaalkylene groups It is linked via the indicated bridging group, which may further contain one or two same or different substituents.
式(I)のメタロセンの好ましい基は、2つのR1基が
シクロペンタジエニル またはC1〜C4−アルキルで置換
されているシクロペンタジエニル であり、R2およびR3
が、式 (式中、R5およびR6は各々独立してHまたはFであり、
R7は式−(CzH2zO)0−R9のポリオキサアルキレンであ
り、フェニル環に直接または式−O−で表わされる架橋
基を介して結合されている。R5およびR6は、好ましくは
Fである。) の基である。 Preferred groups of metallocenes of formula (I) are two R1Group
Cyclopentadienyl Or C1~ CFour-Substituted with alkyl
Cyclopentadienyl And RTwoAnd RThree
Is the expression(Where RFiveAnd R6Is each independently H or F;
R7Is the formula-(CzHTwozO)0−R9Is a polyoxaalkylene
Or a bridge represented by the formula -O-
Linked through a group. RFiveAnd R6Is preferably
F. ).
ポリオキサアルキレン基は好ましくは1〜20個、さら
に好ましくは1〜12個、特に好ましくは2〜6個のオキ
サアルキレン単位を含有するものである。(ポリオキサ
アルキレン)基中のアルキレンは、好ましくは2〜6
個、特に2〜4個の炭素原子を含有するものであり、特
にエチレンまたは1,2−プロピレンを含有するものであ
る。他の具体例は、1,3−プロピレン、1,2−、1,3−、
および1,4−ブチレン、ペンチレンおよびヘキシレンで
ある。ポリオキサアルキレン基は、種々のアルキレン基
を含有することができる。The polyoxaalkylene group preferably contains 1 to 20, more preferably 1 to 12, and particularly preferably 2 to 6, oxaalkylene units. The alkylene in the (polyoxaalkylene) group is preferably 2-6.
And especially those containing 2 to 4 carbon atoms, especially those containing ethylene or 1,2-propylene. Other specific examples are 1,3-propylene, 1,2-, 1,3-,
And 1,4-butylene, pentylene and hexylene. The polyoxaalkylene group can contain various alkylene groups.
式(I)の特に好ましいチタノセンは、R1がシクロペ
ンタジエニルまたはメチルシクロペンタジエニルであ
り、R2およびR3は、式 (式中、R5およびR6は水素または弗素であり、oは2〜
6の数であり、R9はC1〜C12−アルキルである。) のものであつて、特にR5とR6が弗素であるものである。Particularly preferred titanocenes of the formula (I) are those wherein R 1 is cyclopentadienyl or methylcyclopentadienyl and R 2 and R 3 are of the formula Wherein R 5 and R 6 are hydrogen or fluorine, and o is 2-
A number of 6 and R 9 is C 1 -C 12 -alkyl. Wherein R 5 and R 6 are in particular fluorine.
式(I)のチタノセンの具体例を示すと下記の通りで
ある。すなわち、ビス(シクロペンタジエニル)−ビス
〔4−(1′,4′,7′−トリオキサウンデシル)−2,3,
5,6−テトラフルオロフエニル〕−チタニウム、ビス
(メチルシクロペンタジエニル)−ビス〔4−(1′,
4′,7′−トリオキサウンデシル)−2,3,5,6−テトラフ
ルオロフエニル〕−チタニウム、ビス(シクロペンタジ
エニル)−ビス〔4−(1′,4′,7′,10′−テトラオ
キサドデシル)−2,3,5,6−テトラフルオロフエニル〕
−チタニウム、ビス(メチルシクロペンタジエニル)−
ビス〔3−(1′,4′,7′−トリオキサヘンデシル)−
2,6−ジフルオロフエニル〕−チタニウム、ビス(シク
ロペンタジエニル)−ビス〔3−(1′,4′,7′,10′
−トリオキサドデシル)−2,6−トリフルオロフエニ
ル〕−チタニウムおよびビス(シクロペンタジエニル)
−ビス〔3−(1′,4′−ジオキサペンチル)−2,6−
ジフルオロフエニル〕−チタニウムである。Specific examples of the titanocene of the formula (I) are as follows. That is, bis (cyclopentadienyl) -bis [4- (1 ′, 4 ′, 7′-trioxaundecyl) -2,3,
5,6-tetrafluorophenyl] -titanium, bis (methylcyclopentadienyl) -bis [4- (1 ′,
4 ', 7'-trioxaundecyl) -2,3,5,6-tetrafluorophenyl! -Titanium, bis (cyclopentadienyl) -bis [4- (1', 4 ', 7', 10'-tetraoxadodecyl) -2,3,5,6-tetrafluorophenyl
-Titanium, bis (methylcyclopentadienyl)-
Bis [3- (1 ', 4', 7'-trioxahendecyl)-
2,6-difluorophenyl] -titanium, bis (cyclopentadienyl) -bis [3- (1 ', 4', 7 ', 10'
-Trioxadodecyl) -2,6-trifluorophenyl] -titanium and bis (cyclopentadienyl)
-Bis [3- (1 ', 4'-dioxapentyl) -2,6-
Difluorophenyl] -titanium.
式(I)のチタノセンは、式(IV) (式中、R1は上記の通りであり、Zはハロゲンであり、
特にClがよい。) の化合物の1モルを2モルのLiR2(式中R2は上記の通り
である)と反応させ、公知の方法で式(I)の化合物を
単離させることによつて公知の製造法または類似の製造
法によつて製造することができる。The titanocene of the formula (I) has the formula (IV) Wherein R 1 is as described above, Z is halogen,
Especially Cl is good. ) Is reacted with 2 moles of LiR 2 (wherein R 2 is as defined above) and the compound of formula (I) is isolated in a known manner to produce a known process. Or it can be manufactured by a similar manufacturing method.
公知方法は、例えばJ.Organometal.Chem.,2(1964
年)206〜212頁,J.Organometal.Chem.,4(1965年)445
〜446頁およびヨーロツパ特許A−O,122,223中に記載さ
れている。Known methods are described, for example, in J. Organometal. Chem., 2 (1964).
Year) 206-212, J. Organometal. Chem., 4 (1965) 445
446 pages and in European Patent A-0,122,223.
Zが特に塩素である式(IV)の出発物質は公知であ
り、TiCl4をナトリウム化合物のNaR1と反応させる類似
反応によつて得ることができる。リチウム化合物のLiR2
も同様に公知であり、R2−ハライド、特にブロマイドを
ブチルリチウムと反応させる類似反応によつて製造する
ことができる。第3アミノエチル基によつて置換される
誘導体は、例えば、対応するジフルオロジブロモフエニ
ル化合物を、まずリチウムジフルオロブロモフエニル化
合物にし、次にこれをN,N−ジアルキルメチレンアンモ
ニウムクロライドと反応させ、得られたジアルキルアミ
ノメチル−ジフルオロブロモフエニルを、ブチルリチウ
ムと反応させることによつて、対応するリチウム化合物
にする類似方法によつて製造することができる。The starting materials of the formula (IV) in which Z is in particular chlorine are known and can be obtained by a similar reaction in which TiCl 4 is reacted with the sodium compound NaR 1 . LiR 2 for lithium compounds
Are also known and can be prepared by analogous reactions of reacting R 2 -halides, in particular bromide, with butyllithium. Derivatives substituted by a tertiary aminoethyl group may for example be obtained by first converting the corresponding difluorodibromophenyl compound into a lithium difluorobromophenyl compound, which is then reacted with N, N-dialkylmethyleneammonium chloride, The resulting dialkylaminomethyl-difluorobromophenyl can be prepared by a method analogous to the corresponding lithium compound by reacting with butyllithium.
遊離の、またはエーテル化またはエステル化ポリオキ
サアルキレン基は、公知の方法によつてR2−ハライドの
中に導入する。橋基のために適した先駆体を含有する官
能性R2−ハライドは例えば、L.S.Kobrinaによつて、Flu
orine Chemistry Reviews第7巻,1〜114頁(ニユーヨー
クのMarcel Dekker社から1974年発行)中に記載されて
いる。Free or etherified or esterified poly oxaalkylene group, Yotsute R 2 in a known manner - is introduced into the halide. Functional R 2 -halides containing precursors suitable for bridging groups are described, for example, by LS Kobrina in Fluid
orine Chemistry Reviews, Vol. 7, pages 1-114 (issued by Marcel Dekker, New York, 1974).
式(I)のメタロセンは、通常、不活性溶媒の存在下
に、例えば炭化水素またはエーテルの存在下に不活性ガ
ス雰囲気中で−30〜−100℃、好ましくは−60〜90℃の
温度で製造することができる。具体例を示せば、LiR2は
まずエーテル溶媒中で−78℃の温度で、対応するハライ
ドをリチウムブチルと反応させることによつて製造す
る。冷却した反応混合物に対応のチタノセンジハライド
を加え、冷却手段を除去し、混合物を室温まで温める。
必要に応じて、溶媒を添加してから、反応混合物を濾過
し、本発明のチタノセン化合物を沈澱によるかまたは溶
媒の蒸発によつて単離させる。The metallocenes of the formula (I) are usually prepared in the presence of an inert solvent, for example in the presence of a hydrocarbon or ether, in an inert gas atmosphere at a temperature of -30 to -100C, preferably -60 to 90C. Can be manufactured. Illustratively, LiR 2 is prepared by first reacting the corresponding halide with lithium butyl in an ether solvent at a temperature of -78 ° C. The corresponding titanocene dihalide is added to the cooled reaction mixture, the cooling means is removed and the mixture is warmed to room temperature.
If necessary, after addition of a solvent, the reaction mixture is filtered and the titanocene compound of the invention is isolated by precipitation or by evaporation of the solvent.
生成物は通常、液状、樹脂状に至るまでのシロツプ状
であつて通常オレンジ色の化合物ですぐれた熱安定性を
有しており、高温下においてのみ分解する。空気の作用
および水の作用下では分解は認められない。本発明の化
合物は、かなりの多量でも硬化性組成物中に容易に溶解
させることができるか、またはこれらを混合させること
ができるので、使用の際に有利である。本発明の化合物
は溶媒中にも非常にすみやかに溶解させることができ、
硬化性組成物中に溶媒のかたちで混入し、その後、溶媒
を必要に応じて除去してもよい。The product is usually in the form of a liquid or resinous syrup, usually an orange compound having excellent thermal stability and decomposes only at high temperatures. No decomposition is observed under the action of air and water. The compounds of the present invention are advantageous in use because they can be readily dissolved in the curable compositions, or even mixed in significant amounts. The compounds of the invention can also be dissolved very quickly in solvents,
The solvent may be mixed into the curable composition in the form of a solvent, and then the solvent may be removed as necessary.
本発明の化合物は暗所で貯蔵安定性を持ち、不活性ガ
スなしでも取扱うことができる。本発明の化合物はそれ
自身で、エチレン性不飽和化合物の光誘発重合の極めて
有効な光重合開始剤としても非常にすぐれている。すな
わち、200nm(紫外線)〜600nmの広い波長範囲にわたつ
て非常にすぐれた感光性と有効性を有するものである。
本発明のチタノセンはさらに熱の影響下に有効に重合開
始することができ、170℃〜240℃までに加熱するのがよ
い。光の作用および加熱も無論重合に利用することがで
き、重合の際、露光後に加熱すれば、さらに低い温度、
例えば80〜150℃の加熱ですむ。The compounds of the invention have storage stability in the dark and can be handled without inert gases. The compounds according to the invention by themselves are also very good photopolymerization initiators which are very effective for photoinduced polymerization of ethylenically unsaturated compounds. That is, it has extremely excellent photosensitivity and effectiveness over a wide wavelength range from 200 nm (ultraviolet light) to 600 nm.
The titanocenes of the present invention can also initiate polymerization effectively under the influence of heat and are preferably heated to 170-240 ° C. Of course, the action of light and heating can also be used for polymerization, and during polymerization, if heated after exposure, lower temperatures,
For example, heating at 80 to 150 ° C. is sufficient.
本発明のチタノセンは少なくとも1個のエチレン性不
飽和二重結合を有する少なくとも1種の不揮発モノマ
ー、オリゴマーまたはポリマー化合物を放射線重合する
ための開始剤として用いられる。具体的には、(a)1
個以上のエチレン性不飽和二重結合を有する1種以上の
重合性非揮発性モノマー、オリゴマーまたはポリマー化
合物と、(b)光重合開始剤としての1種以上の式
(I)のチタンノセンとを含有する組成物として用いる
のが好ましい。The titanocenes according to the invention are used as initiators for the radiation polymerization of at least one non-volatile monomer, oligomer or polymer compound having at least one ethylenically unsaturated double bond. Specifically, (a) 1
At least one polymerizable non-volatile monomer, oligomer or polymer compound having at least one ethylenically unsaturated double bond, and (b) at least one titanium nocene of the formula (I) as a photopolymerization initiator. It is preferably used as a composition containing.
この組成物は、さらに追加の光重合開始剤(c)を含
有していてもよく例えばベンジルケタール、4−アロイ
ル−1,3−ジオキソラン、ジアルコキシアセトフエノン
またはα−ヒドロキシ−またはα−アミノ−アセトフエ
ノン系またはこれらの混合物を使用できる。有利な点
は、本発明のチタノセンの量をさらに少くすることがで
き、それにもかかわらず同一または改良された感光度が
達成できる点である。成分(c):成分(b)の重量比
は例えば1:1〜30:1、好ましくは5:1〜15:1にすることが
できる。The composition may further comprise an additional photoinitiator (c), for example benzyl ketal, 4-aroyl-1,3-dioxolan, dialkoxyacetophenone or α-hydroxy- or α-amino. Acetophenones or mixtures thereof can be used. An advantage is that the amount of titanocene of the present invention can be further reduced while still achieving the same or improved photosensitivity. The weight ratio of component (c) to component (b) can be, for example, 1: 1 to 30: 1, preferably 5: 1 to 15: 1.
添加させる本発明のチタノセンの量は本質的に経済
性、溶解度および目的とする感光度によつて変化する。
通常は成分(a)を基準とし0.01〜20重量%、好ましく
は0.05〜10重量%、さらに好ましくは0.1〜5重量%で
使用される。The amount of titanocene of the invention added depends essentially on the economics, the solubility and the desired photosensitivity.
Usually, it is used in an amount of 0.01 to 20% by weight, preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the component (a).
使用できる成分(a)は、光重合によつてさらに分子
量の高い製品にすることができ、重合することによりそ
の溶解度を変化させるエチレン性不飽和モノマー、オリ
ゴマーおよびポリマー化合物である。Component (a) which can be used are ethylenically unsaturated monomers, oligomers and polymer compounds which can be converted into higher molecular weight products by photopolymerization and which change their solubility by polymerization.
特に適した化合物は、例えばエチレン性不飽和カルボ
ン酸およびポリオールのエステルまたはポリエポキシ
ド、直鎖中または側鎖基中にエチレン性不飽和基を含む
ポリマー、例えば、不飽和ポリエステル、ポリアミドお
よびポリウレタンおよびこれらのコポリマー、ポリブタ
ジエン、ブタジエンコポリマー、ポリイソプレンおよび
イソプレンコポリマー、側鎖に(メタ)アクリル基を有
するポリマーおよびコポリマー、および1種以上のこの
ようなポリマーの混合物である。Particularly suitable compounds are, for example, esters or polyepoxides of ethylenically unsaturated carboxylic acids and polyols, polymers containing ethylenically unsaturated groups in the linear or pendant groups, such as unsaturated polyesters, polyamides and polyurethanes and the like. Copolymers, polybutadienes, butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers having (meth) acrylic groups in the side chains, and mixtures of one or more such polymers.
不飽和カルボン酸の例としては、アクリル酸、メタク
リル酸、クロトン酸、イタコン酸、桂皮酸、さらにはリ
ノレイン酸またはオレイン酸のような不飽和脂肪酸があ
る。アクリル酸およびメタアクリル酸が好ましい。Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, as well as unsaturated fatty acids such as linoleic acid or oleic acid. Acrylic acid and methacrylic acid are preferred.
適当なポリオールは、芳香族ポリオール、特に脂肪族
ポリオールおよび脂環族ポリオールである。芳香族ポリ
オールの例としては、ハイドロキノン、4,4′−ジヒド
ロキシジフエニル、2,2−ジ(4−ヒドロキシフエニ
ル)−プロパン、ノボラツクおよびレゾールがある。ポ
リエポキシドの例は、上述のポリオールをベースとする
ものであり、特に芳香族ポリオールおよびエピクロロド
リンがある。さらに、ポリマー連鎖または側鎖基にヒド
ロキシル基を含有するポリマーまたはコポリマー、例え
ばポリビニルアルコールおよびそのコポリマー、または
ポリメタクリル酸ヒドロキシルアルキルエステルまたは
これらのコポリマーも、ポリオールとして適している。
他の適切なポリオールは、ヒドロキシ端末基を持つオリ
ゴマーである。Suitable polyols are aromatic polyols, especially aliphatic and cycloaliphatic polyols. Examples of aromatic polyols include hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di (4-hydroxyphenyl) -propane, novolak and resole. Examples of polyepoxides are based on the polyols mentioned above, in particular aromatic polyols and epichlorodrine. Furthermore, polymers or copolymers containing hydroxyl groups in the polymer chains or side groups, such as polyvinyl alcohol and its copolymers, or polyhydroxyalkyl methacrylates or copolymers thereof, are also suitable as polyols.
Other suitable polyols are oligomers having hydroxy terminal groups.
脂肪族および脂環族ポリオールの例としては、エチレ
ングリコール、1,2−または1,3−プロパンジオール、1,
2−、1,3−または1,4−ブタンジオール、ペンタンジオ
ール、ヘキサンジオール、オクタンジオール、ドデカン
ジオール、ジエチレングリコール、トリエチレングリコ
ール、分子量200〜1,500のポリエチレングリコール、1,
3−シクロペンタンジオール、1,2−、1,3−または1,4−
シクロヘキサンジオール、1,4−ジヒドロキシメチルシ
クロヘキサン、グリセロール、トリス−(β−ヒドロキ
シエチル)−アミン、トリメチロールエタン、トリメチ
ロールプロパン、ペンタエリトリトール、ジペンタエリ
トリトールおよびソルビトールのような好ましくは炭素
数2〜12のアルキレンジオールを挙げることができる。Examples of aliphatic and cycloaliphatic polyols include ethylene glycol, 1,2- or 1,3-propanediol,
2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 200 to 1,500,
3-cyclopentanediol, 1,2-, 1,3- or 1,4-
Preferably C2-12, such as cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris-([beta] -hydroxyethyl) -amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. Can be mentioned.
ポリオールは、1種以上の不飽和カルボン酸で部分的
にまたは完全にエステル化されているものであつてもよ
く、また、部分エステル中の遊離のヒドロキシル基につ
いて、例えばエーテル化するとか、他のカルボン酸でエ
ステル化することにより変性を行つてもよい。The polyol may be partially or completely esterified with one or more unsaturated carboxylic acids, and may be freed from free hydroxyl groups in the partial ester, for example by etherification or other Modification may be performed by esterification with a carboxylic acid.
エステルの例としては、トリメチロールプロパントリ
アクリレート、トリメチロールエタントリアクリレー
ト、トリメチロールプロパントリメタクリレート、トリ
メチロールエタントリメタクリレート、テトラメチレン
グリコールジメタクリレート、トリエチレングリコール
ジメタクリレート、テトラエチレングリコールジアクリ
レート、ペンタエリトリトールジアクリレート、ペンタ
エリトリトールトリアクリレート、ペンタエリトリトー
ルテトラアクリレート、ジペンタエリトリトールジアク
リレート、ジペンタエリトリトールトリアクリレート、
ジペンタエリトリトールテトラアクリレート、ジペンタ
エリトリトールペンタアクリレート、ジペンタエリトリ
トールヘキサアクリレート、トリペンタエリトリトール
オクタアクリレート、ペンタエリトリトールジメチルア
クリレート、ペンタエリトリトールトリメタクリレー
ト、ジペンタエリトリトールジメタクリレート、ジペン
タエリトリトールテトラメタクリレート、トリペンタエ
リトリトールオクタメタクリレート、ペンタエリトリト
ールジイタコネート、ジペンタエリトリオールトリスイ
タコネート、ジペンタエリトリトールペンタイタコネー
ト、ジペンタエリトリトールヘキサイタコネート、エチ
レングリコールジメタクリレート、1,3−ブタンジオー
ルジアクリレート、1,3−ブタンジオールジメタクリレ
ート、1,4−ブタンジオールジイタコネート、ソルビト
ールトリアクリレート、ソルビトールテトラアクリレー
ト、ソルビトールテトラメタクリレート、ソルビトール
ペンタクリレート、ソルビトールヘキサアクリレート、
オリゴエステルアクリレートおよびメタクリレート、グ
リセロール、ジ−およびトリアクリレート、1,4−シク
ロヘキサンジアクリレート、分子量200〜1,500のポリエ
チレングリコールのビスアクリレートおよびビスメタク
リレートまたはこれらの混合物がある。Examples of the ester include trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and pentaerythritol. Diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate,
Dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethyl acrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octa Methacrylate, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentitaconate, dipentaerythritol hexaitaconate, ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol Dimethacrylate, 1,4-butanediol Jiitakoneto, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate chestnut rates, sorbitol hexaacrylate,
There are oligoester acrylates and methacrylates, glycerol, di- and triacrylates, 1,4-cyclohexanediacrylate, bisacrylates and bismethacrylates of polyethylene glycol with a molecular weight of 200 to 1,500 or mixtures thereof.
適当な成分(a)は、好ましくは2〜6の、特に2〜
4のアミノ基を持つ芳香族、脂環族、脂肪族ポリアミン
の、同一または異なる不飽和カルボン酸のアミドでもあ
る。このようなポリアミンの例としては、エチレンジア
ミン、1,2−または1,3−プロピレンジアミン、1,2−、
1,3−または1,4−ブチレンジアミン、1,5−ペンチレン
ジアミン、1,6−ヘキシレンジアミン、オクチレンジア
ミン、ドデシレンジアミン、1,4−ジアミノシクロヘキ
サン、イソホロンジアミン、フエニレンジアミン、ビス
−フエニレンジアミン、ジ−β−アミノエチルエーテ
ル、ジエチレントリアミン、トリエチレンテトラミンお
よびジ−(β−アミノエトキシ)−またはジ−(β−ア
ミノプロポキシ)−エタンがある。他の適当なポリアミ
ンは側鎖にアミノ基のあるポリマーおよびコポリマー、
およびアミノ端末基を持つオリゴアミドである。Suitable components (a) are preferably 2 to 6, especially 2 to
It is also an amide of the same or different unsaturated carboxylic acids of aromatic, alicyclic and aliphatic polyamines having 4 amino groups. Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-,
1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine , Bis-phenylenediamine, di-β-aminoethyl ether, diethylenetriamine, triethylenetetramine and di- (β-aminoethoxy)-or di- (β-aminopropoxy) -ethane. Other suitable polyamines are polymers and copolymers having amino groups in the side chain,
And an oligoamide having an amino terminal group.
このような不飽和アミドの例には、メチレン−ビス−
アクリルアミド、1,6−ヘキサメチレン−ビス−アクリ
ルアミド、ジエチレン−トリアミン−トリス−メチルア
クリルアミド、ビス(メタクリルアミド−プロポキシ)
エタン、β−メタクリルアミドエチルメタクリレートお
よびN〔β−ヒドロキシエトキシ)エチル〕−アクリル
アミドがある。Examples of such unsaturated amides include methylene-bis-
Acrylamide, 1,6-hexamethylene-bis-acrylamide, diethylene-triamine-tris-methylacrylamide, bis (methacrylamide-propoxy)
There are ethane, β-methacrylamidoethyl methacrylate and N [β-hydroxyethoxy) ethyl] -acrylamide.
不飽和ポリエステルおよびポリアミドとして適するも
のは、例えば、マレイン酸とジオールまたはジアミンか
ら導びかれるものである。マレイン酸はその一部を他の
ジカルボン酸に置きかえることもできる。エチレン性不
飽和コモノマー、例えばスチレンを一緒に使用したもの
であつてもよい。ポリエステルおよびポリアミドは、ジ
カルボン酸とエチレン性不飽和ジオールまたはジアミ
ン、特に例えば6〜20個の炭素原子を含む、長鎖化合物
から導びかれたものであつてもよい。ポリウレタンの例
としては、飽和または不飽和ジイソシアネートと不飽和
または飽和のジオールから製造されたものがある。Suitable as unsaturated polyesters and polyamides are, for example, those derived from maleic acid and diols or diamines. Maleic acid can be partially replaced by other dicarboxylic acids. It is also possible to use ethylenically unsaturated comonomers, for example styrene, together. Polyesters and polyamides may be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially long-chain compounds containing, for example, 6 to 20 carbon atoms. Examples of polyurethanes are those made from saturated or unsaturated diisocyanates and unsaturated or saturated diols.
ポリブタジエンおよびポリイソプレンおよびこれらの
コポリマーが公知である。コポリマーの例として適する
ものとしては、例えばエチレン、プロペン、ブテン、ヘ
キセン、(メタ)アクリレート、アクリロニトリル、ス
チレンまたは塩化ビニルとのコポリマーである。Polybutadienes and polyisoprenes and their copolymers are known. Suitable as examples of copolymers are, for example, copolymers with ethylene, propene, butene, hexene, (meth) acrylate, acrylonitrile, styrene or vinyl chloride.
側鎖中に(メタ)アクリレート基を持つポリマーも公
知である。これらのポリマーは例えばノボラツク系エポ
キシ樹脂の(メタ)アクリル酸との反応生成物、(メ
タ)アクリル酸でエステル化されたポリビニルアルコー
ルまたはそのアルキル誘導体のホモ−およびコポリマ
ー、ヒドロキシアルキル(メタ)アクリレートでエステ
ル化された(メタ)アクリレートのホモ−およびコポリ
マーである。Polymers having (meth) acrylate groups in the side chains are also known. These polymers are, for example, the reaction products of novolak epoxy resins with (meth) acrylic acid, homo- and copolymers of polyvinyl alcohol or its alkyl derivatives esterified with (meth) acrylic acid, hydroxyalkyl (meth) acrylates. Esterified (meth) acrylate homo- and copolymers.
光重合性化合物は、それら自体として使用してもよ
く、所望の混合物として使用してもよい。ポリオール
(メタ)アクリレートの混合物が好ましい。The photopolymerizable compounds may be used as such or as a desired mixture. Mixtures of polyol (meth) acrylates are preferred.
この組成物には結合剤を添加してもよく、特に光重合
性化合物が液状または粘着性物質である場合には添加す
るとよい。結合剤の量は、全組成物を基準として、例え
ば5〜95重量%特に好ましくは50〜90重量%である。結
合剤は用途分野および水性および有機溶媒系における現
像のしやすさ、基体への接着性、および酸素への感受性
といつた、用途により必要とされる特性により選択され
る。A binder may be added to this composition, particularly when the photopolymerizable compound is a liquid or sticky substance. The amount of binder is, for example, from 5 to 95% by weight, based on the total composition, particularly preferably from 50 to 90% by weight. The binder is chosen according to the properties required by the application, such as the field of application and the ease of development in aqueous and organic solvent systems, adhesion to substrates, and sensitivity to oxygen.
結合剤として適するものの例としては、5,000〜2,00
0,000、好ましくは10,000〜1,000,000の分子量のポリマ
ーである。例としては、メチルメタクリレート/エチル
アクリレート/メタクリル酸のコポリマー、ポリ(メタ
クリル酸アルキルエステル)およびポリ(アクリル酸ア
ルキルエステル)のようなアクリレートおよびメタクリ
レートのホモ−およびコポリマー;酢酸セルロース、セ
ルロースアセトブチレート、メチルセルロースおよびエ
チルセルロースのようなセルロースエステルおよびセル
ロースエーテル;ポリビニルブチラール、ポリビニルホ
ルマール、環化ラバーおよび、ポリエチレンオキシド、
ポリプロピレンオキシドおよびポリテトラヒドロフラン
のようなポリエーテル;ポリスチレン、ポリカーボネー
ト、ポリウレタン、塩素化ポリオレフイン、ポリ塩化ビ
ニル、塩化ビニル;塩化ビニリデンコポリマー、塩化ビ
ニリデンと、アクリロニトリル、メチルメタクリレート
または酢酸ビニルとのコポリマー、ポリ酢酸ビニル、エ
チレン/酢酸ビニルコポリマー、ポリカプロラタムおよ
びポリ(ヘキサメチレンジアジパミド)のようなポリア
ミド、およびポリ(エチレングリコールテレフタレー
ト)およびポリ(ヘキサメチレングリコールスクシネー
ト)のようなポリエステルがある。Examples of suitable binders include 5,000 to 2,000
It is a polymer having a molecular weight of 10,000, preferably 10,000 to 1,000,000. Examples include homo- and copolymers of acrylates and methacrylates such as methyl methacrylate / ethyl acrylate / methacrylic acid copolymers, poly (alkyl methacrylates) and poly (alkyl acrylates); cellulose acetate, cellulose acetobutyrate, Cellulose esters and cellulose ethers such as methylcellulose and ethylcellulose; polyvinyl butyral, polyvinyl formal, cyclized rubber and polyethylene oxide;
Polyethers such as polypropylene oxide and polytetrahydrofuran; polystyrene, polycarbonate, polyurethane, chlorinated polyolefin, polyvinyl chloride, vinyl chloride; vinylidene chloride copolymer, copolymer of vinylidene chloride with acrylonitrile, methyl methacrylate or vinyl acetate, polyvinyl acetate , Ethylene / vinyl acetate copolymers, polyamides such as polycaprolatum and poly (hexamethylenediadipamide), and polyesters such as poly (ethylene glycol terephthalate) and poly (hexamethylene glycol succinate).
この組成物は、例えば木、紙、セラミック、ポリエス
テルおよび酢酸セルロースフイルムのようなプラスチツ
クス、銅およびアルミニウムのような金属のすべてのタ
イプの基体へのコーテイング剤として有用であり、これ
らの場合保護層または写真画像は重合によつて施され
る。本発明はさらに、被覆された基体、および基体に光
重合性画像を施すための方法にも関するものである。The compositions are useful as coatings on all types of substrates, e.g. wood, paper, ceramics, plastics such as polyester and cellulose acetate films, metals such as copper and aluminum, in which case the protective layer Alternatively, the photographic images are applied by polymerization. The invention further relates to a coated substrate and a method for applying a photopolymerizable image to the substrate.
基体は、基体に液状組成物、溶液または懸濁液を塗布
することによつて被覆することができる。溶媒なしの液
状組成物が好ましい。本発明のチタノセンは、他の光重
合開始剤、例えばベンジルケタール、4−アロイル−1,
3−ジオキソラン、ジアルコキシアセトフエノン、α−
ヒドロキシ−またはα−アミノアセトフエノンまたはこ
れらの混合物を含有する液状光重合開始剤混合物の形態
で使用するのがよい。液体から固体状の光重合開始剤を
液体状チタノセンの混合物、または液体状の光重合開始
剤とシロツプ状から固体状のチタノセンの混合物が特に
好ましい。このような混合物は、特に実用上有利であ
り、暗所に貯蔵した場合、すぐれた安定性を示す。The substrate can be coated by applying a liquid composition, solution or suspension to the substrate. Liquid compositions without solvent are preferred. The titanocenes of the present invention may contain other photoinitiators, such as benzyl ketal, 4-aroyl-1,
3-dioxolan, dialkoxyacetophenone, α-
It is preferably used in the form of a liquid photopolymerization initiator mixture containing hydroxy- or α-aminoacetophenone or a mixture thereof. A liquid to solid photopolymerization initiator is particularly preferably a mixture of liquid titanocene, or a mixture of a liquid photopolymerization initiator and syrup to solid titanocene. Such mixtures are particularly practically advantageous and exhibit excellent stability when stored in the dark.
ベンジルケタールの例としては、式 (式中、R13=R14=−CH3、−CH2CH3、−(CH2)2CH3、
−(CH2)3CH3、−CH2CH2CH(CH3)2、 −(CH2)9CH3、−C10H21−iso、 −C12H25−n、−C9H19〜−C11H23混合物、 −CH12−H25〜−C15H31混合物、−CH2CH=CH2、 −CH(CH3)CH=CH2、−CH2CH2OC3H7−iso、 −CH2CH2OC4H9、−CH2CH2OCH2CH=CH2、 −CH(CH3)−CH2OC4H9、−CH2COOCH3、−CH2COOC4H9、 −CH(CH3)COOCH3、−CH2CH2COOC2H5、 −CH(CH3)CH2COOCH3、−CH2CH2CH(CH3)OCH3、 −(CH2CH2O)2CH3、 −(CH2CH2O)2C2H5、−(CH2CH2O)2C4H9、 −(CH2CH2O)3CH3、−(CH2CH2O)3C2H5、 −(CH2CH2O)3C2H5、−(CH2CH2O)3C12H25、 −(CH2CH2O)5C10H21、−(CH2CH2O)8−C9H19〜−C
11H23(混合物)、 −CH2CH2N(C2H5)2、 であるか、R14=−CH3でありR13=−C6H13であるか、R
14=−CH3であり、R13=−C10H21であるか、R14=−CH3
であり、R13=(−CH2CH2O)3C12H25〜−C15H31(混合
物)であるか、R14=−CH3であり、R13=(−CH2CH2O)
5C9H19〜−C11H23(混合物)であるか、またはR14=−C
H3であり、 である。) で示されるものがある。Examples of benzyl ketals have the formula (Where R 13 = R 14 = -CH 3 , -CH 2 CH 3 ,-(CH 2 ) 2 CH 3 ,
− (CH 2 ) 3 CH 3 , −CH 2 CH 2 CH (CH 3 ) 2 , - (CH 2) 9 CH 3 , -C 10 H 21 -iso, -C 12 H 25 -n, -C 9 H 19 ~-C 11 H 23 mixture, -CH 12 -H 25 ~-C 15 H 31 mixture, -CH 2 CH = CH 2, -CH (CH 3) CH = CH 2, -CH 2 CH 2 OC 3 H 7 -iso, -CH 2 CH 2 OC 4 H 9, -CH 2 CH 2 OCH 2 CH = CH 2, -CH (CH 3) -CH 2 OC 4 H 9, -CH 2 COOCH 3, -CH 2 COOC 4 H 9, -CH (CH 3) COOCH 3, -CH 2 CH 2 COOC 2 H 5, -CH (CH 3) CH 2 COOCH 3, -CH 2 CH 2 CH (CH 3) OCH 3, − (CH 2 CH 2 O) 2 CH 3 , − (CH 2 CH 2 O) 2 C 2 H 5 , − (CH 2 CH 2 O) 2 C 4 H 9 , − (CH 2 CH 2 O) 3 CH 3, - (CH 2 CH 2 O) 3 C 2 H 5, - (CH 2 CH 2 O) 3 C 2 H 5, - (CH 2 CH 2 O) 3 C 12 H 25, - (CH 2 CH 2 O) 5 C 10 H 21, - (CH 2 CH 2 O) 8 -C 9 H 19 ~-C
11 H 23 (mixture), —CH 2 CH 2 N (C 2 H 5 ) 2 , Or R 14 = -CH 3 and R 13 = -C 6 H 13 or R
14 = a -CH 3, or a R 13 = -C 10 H 21, R 14 = -CH 3
And R 13 = (— CH 2 CH 2 O) 3 C 12 H 25 to —C 15 H 31 (mixture) or R 14 = —CH 3 and R 13 = (− CH 2 CH 2 O)
5 C 9 H 19 ~-C 11 H 23 ( mixture) a whether or R 14 = -C,
It is H 3, It is. ).
4−アロイル−1,3−ジオキソランの例としては、4
−ベンゾイル−2,2,4−トリメチル−1,3−ジオキソラ
ン、4−ベンゾイル−4−メチル−2,2−テトラメチレ
ン−1,3−ジオキソラン、4−ベンゾイル−4−メチル
−2,2−ペンタメチレン−1,3−ジオキソラン、シス−ト
ランス−4−ベンゾイル−2,4−ジメチル−2−メトキ
シメチル−1,3−ジオキソラン、シス−トランス−4−
ベンゾイル−4−メチル−2−フエニル−1,3−ジオキ
ソラン、4−(4−メトキシベンゾイル)−2,2,4−ト
リメチル−1,3−ジオキソラン、4−(4−メトキシベ
ンゾイル)−4−メチル−2,2−ペンタメチレン−1,3−
ジオキソラン、4−(4−メチルベンゾイル)−2,2,4
−トリメチル−1,3−ジオキソラン、シス−トランス−
4−ベンゾイル−2−メチル−4−フエニル−1,3−ジ
オキソラン、4−ベンゾイル−2,2,4,5,5−ペンタメチ
ル−1,3−ジオキソラン、シス−トランス−4−ベンゾ
イル−2,2,4,5−テトラメチル−1,3−ジオキソラン、シ
ス−トランス−4−ベンゾイル−4−メチル−2−フエ
ニル−1,3−ジオキソラン、シス−トランス−4−ベン
ゾイル−2−ベンゾイル−2,4−ジメチル−1,3−ジオキ
ソラン、シス−トランス−4−ベンゾイル−2−(2−
フリル)−4−メチル−1,3−ジオキソラン、シス−ト
ランス−4−ベンゾイル−5−フエニル−2,2,4−トリ
メチル−1,3−ジオキソランおよび4−(4−メトキシ
ベンゾイル)−2,2,4,5,5−ペンタメチル−1,3−ジオキ
ソランがある。An example of 4-aroyl-1,3-dioxolane is 4
-Benzoyl-2,2,4-trimethyl-1,3-dioxolan, 4-benzoyl-4-methyl-2,2-tetramethylene-1,3-dioxolan, 4-benzoyl-4-methyl-2,2- Pentamethylene-1,3-dioxolan, cis-trans-4-benzoyl-2,4-dimethyl-2-methoxymethyl-1,3-dioxolan, cis-trans-4-
Benzoyl-4-methyl-2-phenyl-1,3-dioxolan, 4- (4-methoxybenzoyl) -2,2,4-trimethyl-1,3-dioxolan, 4- (4-methoxybenzoyl) -4- Methyl-2,2-pentamethylene-1,3-
Dioxolan, 4- (4-methylbenzoyl) -2,2,4
-Trimethyl-1,3-dioxolan, cis-trans-
4-benzoyl-2-methyl-4-phenyl-1,3-dioxolan, 4-benzoyl-2,2,4,5,5-pentamethyl-1,3-dioxolan, cis-trans-4-benzoyl-2, 2,4,5-tetramethyl-1,3-dioxolan, cis-trans-4-benzoyl-4-methyl-2-phenyl-1,3-dioxolan, cis-trans-4-benzoyl-2-benzoyl-2 , 4-Dimethyl-1,3-dioxolan, cis-trans-4-benzoyl-2- (2-
Furyl) -4-methyl-1,3-dioxolan, cis-trans-4-benzoyl-5-phenyl-2,2,4-trimethyl-1,3-dioxolan and 4- (4-methoxybenzoyl) -2, There is 2,4,5,5-pentamethyl-1,3-dioxolan.
ジアルコキシアセトフエノンの例としては、α,α−
ジメトキシアセトフエノン、α,α−ジエトキシアセト
フエノン、α,α−ジ−イソプロポキシアセトフエノ
ン、α,α−ジ−(2−メトキシエトキシ)アセトフエ
ノン、α−ブトキシ−α−エトキシアセトフエノン、
α,α−ジブトキシ−4−クロロアセトフエノン、α,
α−ジエトキシ−4−フルオロアセトフエノン、α,α
−ジメトキシ−4−メチルアセトフエノン、α,α−ジ
メトキシ−4−メチルアセトフエノン、α,α−ジメト
キシプロピオフエノン、α,α−ジエトキシプロピオフ
エノン、α,α−ジエトキシブチロフエノン、α,α−
ジメトキシイソバレロフエノン、α,α−ジエトキシ−
α−シクロヘキシルアセトフエノンおよびα,α−ジプ
ロポキシ−4−クロロプロピオフエノンがある。Examples of dialkoxyacetophenone include α, α-
Dimethoxyacetophenone, α, α-diethoxyacetophenone, α, α-di-isopropoxyacetophenone, α, α-di- (2-methoxyethoxy) acetophenone, α-butoxy-α-ethoxyacetophene Non,
α, α-dibutoxy-4-chloroacetophenone, α,
α-diethoxy-4-fluoroacetophenone, α, α
-Dimethoxy-4-methylacetophenone, α, α-dimethoxy-4-methylacetophenone, α, α-dimethoxypropiophenone, α, α-diethoxypropiophenone, α, α-diethoxybutyrov Enone, α, α-
Dimethoxyisovalerophenone, α, α-diethoxy-
There are α-cyclohexylacetophenone and α, α-dipropoxy-4-chloropropiophenone.
α−ヒドロキシ−およびα−アミノアセトフエノンの
例としては、2−ヒドロキシ−2−メチル−1−フエニ
ル−プロパン−1−オン、2−ヒドロキシ−2−エチル
−1−フエニルヘキサン−1−オン、1−(4−ドデシ
ルフエニル)−2−ヒドロキシ−2−メチルプロパン−
1−オン、1−(2,4−ジメチルフエニル)−2−ヒド
ロキシ、−2−メチルプロパン−1−オン、2−ヒドロ
キシ−1−(4−メトキシフエニル)−2−メチルプロ
パン−1−オン、2−ヒドロキシ−2−メチル−1−フ
エニルブタン−1−オン、2−ジメチルアミノ−2−メ
チル−1−フエニルプロパン−1−オン、2−ブチルア
ミノ−2−メチル−1−フエニルプロパン−1−オン、
1−(4−フルオロフエニル)−2−メチル−2−モル
ホリノペンタン−1−オン、2−メチル−1−(4−メ
チルチオフエニル)−2−モルホリノブタン−1−オ
ン、2−ジメチルアミノ−1−(4−メトキシフエニル
(−2−メチルプロパン−1−オンおよび2−ジエチル
アミノ−1−(4−ジエチルアミノフエニル)−2−メ
チルプロパン−1−オンがある。Examples of α-hydroxy- and α-aminoacetophenones include 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-hydroxy-2-ethyl-1-phenylhexane-1-. On, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-
1-one, 1- (2,4-dimethylphenyl) -2-hydroxy, 2-methylpropan-1-one, 2-hydroxy-1- (4-methoxyphenyl) -2-methylpropane-1 -One, 2-hydroxy-2-methyl-1-phenylbutan-1-one, 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-butylamino-2-methyl-1-phenyl Enylpropan-1-one,
1- (4-fluorophenyl) -2-methyl-2-morpholinopentan-1-one, 2-methyl-1- (4-methylthiophenenyl) -2-morpholinobtan-1-one, 2-dimethylamino There are -1- (4-methoxyphenyl (-2-methylpropan-1-one) and 2-diethylamino-1- (4-diethylaminophenyl) -2-methylpropan-1-one.
光重合開始剤混合物(b)+(c)を、成分(a)を
基準として、0.5〜20重量%、好ましくは1〜10重量%
の量で添加する。0.5 to 20% by weight, preferably 1 to 10% by weight, based on the component (a), of the photopolymerization initiator mixture (b) + (c)
Add in the amount of
溶媒およびその濃度の選択は主として組成物の特性お
よびその塗布方法によつて選択することができる。本発
明の組成は、公知手段例えば浸漬法、ナイフコーテイン
グ法、カーテンコーテイング法、電着法、ブラシ法、ス
プレー法または逆ロールコーテイング法によつて基体上
に均一に塗布することができる。塗布する厚さ(塗膜厚
さ)および基体(担持層)の特性は、目的とする利用分
野によつて決まる。The choice of the solvent and its concentration can be selected mainly depending on the properties of the composition and its application method. The composition of the present invention can be uniformly applied to a substrate by a known means such as a dipping method, a knife coating method, a curtain coating method, an electrodeposition method, a brush method, a spray method or a reverse roll coating method. The thickness to be applied (coat thickness) and the properties of the substrate (support layer) are determined by the intended field of use.
例えば、情報の写真記録用の場合には、担持層として
は、ポリエステルフイルム、酢酸セルロースフイルムま
たはプラスチツクで被覆された紙が使用される。オフセ
ツト印刷版用の場合には、特殊処理したアルミニウムが
使用され、プリント回路の場合には銅を張つた積層物が
使用される。写真材料およびオフセツト印刷版の場合の
層の厚さは通常0.5〜10μmであり、プリント回路の場
合は通常、1〜100μmである。溶媒を使用することも
できるが、この場合塗布後に除去される。For example, in the case of photographic recording of information, a paper coated with a polyester film, a cellulose acetate film or a plastic is used as the carrier layer. For offset printing plates, specially treated aluminum is used, and for printed circuits, copper-clad laminates are used. For photographic materials and offset printing plates, the layer thickness is usually 0.5 to 10 μm, and for printed circuits it is usually 1 to 100 μm. Solvents can be used, but are removed after application.
種々の目的に使用されるような光重合組成物は、通
常、光重合性化合物を光重合開始剤に加えて、他の添加
剤も含有している。成分を混合して組成物を製造する間
の早期重合を防止する目的で熱安定剤を添加することが
慣用的に行われている。このような目的に使用される熱
安定剤としては、例えばハイドロキノン、ハイドロキノ
ン誘導体、p−メトキシフエノール、β−ナフトールま
たは例えば2,6−ジ(第3−ブチル)p−クレゾールの
ような立体障害のあるフエノールがある。少量の紫外線
吸収剤、例えばベンゾトリアゾール、ベンゾフエノンま
たはオキサルアニリドタイプのものを、さらに添加して
もよい。立体障害アミンタイプ(HALS)の光安定剤を添
加してもよい。The photopolymerizable composition used for various purposes usually contains a photopolymerizable compound and other additives in addition to the photopolymerization initiator. It is customary to add heat stabilizers to prevent premature polymerization during the mixing of the components to produce the composition. Examples of the heat stabilizer used for this purpose include steric hindrance such as hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol or 2,6-di (tert-butyl) p-cresol, for example. There is a certain phenol. A small amount of UV absorbers, for example of the benzotriazole, benzophenone or oxalanilide type, may also be added. A sterically hindered amine type (HALS) light stabilizer may be added.
ナフテン酸銅、ステアリン酸銅、オクタン酸銅のよう
な銅化合物;トリフエニルホスフイン、トリブチルホス
フイン、トリエチルホスフイン、トリフエニルホスフア
イトまたはトリベンゾイルホスフアイトのようなリン化
合物;テトラメチルアンモニウムクロライド、またはト
リメチルベンゾイルアンモニウムクロライドのような第
4級アンモニウム化合物;またはN−ジエチルヒドロキ
シアミンのようなヒドロキシアミン誘導体も暗所貯蔵安
定性を増すために添加することができる。Copper compounds such as copper naphthenate, copper stearate, copper octoate; phosphorus compounds such as triphenylphosphine, tributylphosphine, triethylphosphine, triphenylphosphite or tribenzoylphosphite; tetramethylammonium chloride; Alternatively, a quaternary ammonium compound such as trimethylbenzoyl ammonium chloride; or a hydroxyamine derivative such as N-diethylhydroxyamine can also be added to increase dark storage stability.
空中酸素の悪影響を排除するために光硬化性混合物に
パラフインや同様のワツクス状物質を添加することもし
ばしば行われている。重合が開始すると、これらの物質
はポリマー中への溶解性がないために浮き出て、空気の
出入りを防止する透明な表面層を形成する。It is also common to add paraffin or similar waxy materials to the photocurable mixture to eliminate the adverse effects of atmospheric oxygen. When polymerization begins, these materials emerge due to their insolubility in the polymer, forming a transparent surface layer that prevents air from entering and leaving.
その他の慣用添加剤としては、特定の波長において吸
収し、吸収したエネルギーを重合開始剤に放出するか、
それ自身で補助重合開始剤として作用する光増感剤があ
る。これらの例としてはチオキサントン、アントラセ
ン、アントラキノンおよびクマリン誘導体がある。Other conventional additives include absorbing at a specific wavelength and releasing the absorbed energy to a polymerization initiator,
There are photosensitizers that themselves act as auxiliary polymerization initiators. Examples of these are thioxanthone, anthracene, anthraquinone and coumarin derivatives.
他の慣用の添加剤としてはアミンタイプの促進剤があ
り、これは連鎖移動剤として作用するので着色配合物中
において特に重要である。これらの例としては、N−メ
チルジエタノールアミン、トリエチルアミン、エチルp
−ジメチルアミノベンゾエートまたはミヒラーのケトン
がある。このようなアミンの作用は、ベンゾフエノンタ
イプの芳香族ケトンの添加によつて強化されることがで
きる。Other conventional additives include accelerators of the amine type, which are particularly important in colored formulations as they act as chain transfer agents. Examples of these include N-methyldiethanolamine, triethylamine, ethyl p
Dimethylaminobenzoate or Michler's ketone. The action of such amines can be enhanced by the addition of aromatic ketones of the benzophenone type.
その他の慣用添加剤としては、充填剤、顔料、染料、
接着剤、保湿剤、流れ調整剤がある。Other conventional additives include fillers, pigments, dyes,
There are adhesives, humectants, flow regulators.
印刷インクの場合、光硬化は非常に重要であり、接着
剤の乾燥時間は、写真製造の製造速度にとつて決定的要
素であり、秒単位でなくてはならない。紫外線硬化性印
刷インクはスクリーン印刷用としては特に有用である。In the case of printing inks, photocuring is very important and the drying time of the adhesive is a crucial factor for the production speed of photographic production and must be in seconds. Ultraviolet curable printing inks are particularly useful for screen printing.
この光硬化性組成物は印刷版、特に可撓性印刷版の製
造に適しており、この用途には、例えば可溶性線状のポ
リアミドまたはスチレン−ブタジエンゴムと、例えばア
クリルアミドまたはアクリレートのような光重合性モノ
マーとの混合物と、光重合開始剤が、使用される。この
ような系のフイルムと、ネガ(またはポジ)のプリント
マスターを介して露光され、非硬化部分を溶媒で流去さ
せる。The photocurable compositions are suitable for the production of printing plates, in particular flexible printing plates, for this purpose, for example, with soluble linear polyamides or styrene-butadiene rubbers and with photopolymerizations such as, for example, acrylamide or acrylates. A mixture with a hydrophilic monomer and a photopolymerization initiator are used. Exposure through a film of such a system and a negative (or positive) print master causes the uncured portions to run off with the solvent.
光硬化を利用する他の分野としては、例えば管用、か
ん用、びんキヤツプ用のシート金属用のワニスがけとい
つたような、金属の被覆、およびポリ塩化ビニルベース
の床および壁被覆のような、プラスチツクの被覆の光硬
化がある。Other areas of application of light curing include metal coatings, such as varnishing for sheet metal for tubes, cans, bottle caps, and floor and wall coatings based on polyvinyl chloride. , There is light curing of the plastic coating.
紙上のコーテイングの光硬化の例は、ラベルの無色ワ
ニス、レコードの袋および本のジヤケツトである。Examples of photocuring of coatings on paper are colorless varnishes for labels, record bags and book jackets.
画像製造用および情報担体の光学製品用の光硬化性組
成物の利用も重要である。この場合担体に塗布した層
(湿つたまたは乾燥した)に、短波長光をフオトマスク
を通して照射し、塗膜の露光されなかつた帯域を溶媒
(現像液)で処理して除去する。露光帯域は架橋ポリマ
ーであるので不溶性であり、担体上に残留する。担体が
金属層である場合、露光および現像後、金属をエツチン
グ除去し、非露光帯域上で電気メツキすることによつて
厚くさせる。プリント回路およびフオトレジストはこの
ようにして製造される。The use of photocurable compositions for image production and for optical products as information carriers is also important. In this case, the layer (wet or dried) applied to the carrier is irradiated with short-wavelength light through a photomask, and the unexposed zones of the coating are removed by treatment with a solvent (developer). The exposed zone is insoluble because it is a crosslinked polymer and remains on the carrier. If the support is a metal layer, after exposure and development, the metal is etched away and thickened by electroplating over the non-exposed zones. Printed circuits and photoresists are manufactured in this way.
露光のために適した光源は、短波長光を高含有率で含
むものがよい。適当な技術装置および種々のタイプのラ
ンプは入手可能である。例えばカーボンアークランプ、
キセノンアークランプ、水銀蒸気ランプ、金属−ハロゲ
ノランプ、蛍光ランプ、アルゴンランプまたは写真用投
光照射ランプがある。レーザー光線源も最近では使用さ
れている。レーザー光線の場合には、フオトマスクを必
要としない点で有利であり、調整されたレーザー光線で
光硬化性層上に直接写字する。A light source suitable for exposure preferably has a high content of short wavelength light. Suitable technical equipment and various types of lamps are available. For example, carbon arc lamp,
There is a xenon arc lamp, a mercury vapor lamp, a metal-halogeno lamp, a fluorescent lamp, an argon lamp or a floodlight lamp for photography. Laser beam sources have also been used recently. In the case of a laser beam, it is advantageous in that a photomask is not required, and the character is directly copied onto the photocurable layer with the adjusted laser beam.
本発明のチタノセンは光硬化性組成物の成分を容易に
混合できるか、組成物中に容易に溶解でき、従つてすぐ
れた感光性を達成することができる。The titanocene of the present invention can be easily mixed with the components of the photocurable composition or can be easily dissolved in the composition, thereby achieving excellent photosensitivity.
以下の実施例において、本発明をさらに具体的に説明
する。The present invention will be described more specifically in the following examples.
実施例1 a)ジエチレングリコールモノ−ブチルモノ−(2,3,5,
6−テトラフルオロ−4−クロロ)−フエニルエーテル
の製造 500mlのジエチレングリコールモノブチルエーテルの
中に23gの細かく切つたナトリウム金属(1モル)を入
れ、混合物の温度を、外側を冷却することによつて約45
℃に保持した。反応がおさまつてから、混合物をナトリ
ウムが完全に溶解するまで50℃までに温めた。この茶色
の溶液を1時間かけて、40〜45℃で233gのクロロペンタ
フルオロベンゼン(1,16モル)中に注入した。反応混合
物を70℃まで加熱し、この温度で約7時間保つた。冷却
後、1の水の中に注ぎ込み、1のメチレンクロライ
ドで抽出した。有機層を分離し、Na2SO4を乾燥し、溶媒
を水流ポンプ真空下に蒸留した。残留物を高真空下に精
留し、3ミリバール下に100〜104℃で沸騰する留分を集
めた。280gの透明無色の油が得られた。Example 1 a) Diethylene glycol mono-butyl mono- (2,3,5,
Preparation of 6-tetrafluoro-4-chloro) -phenyl ether 23 g of minced sodium metal (1 mol) are placed in 500 ml of diethylene glycol monobutyl ether and the temperature of the mixture is reduced by cooling the outside. About 45
C. was maintained. After the reaction had subsided, the mixture was warmed to 50 ° C. until the sodium was completely dissolved. The brown solution was poured into 233 g of chloropentafluorobenzene (1,16 mol) at 40-45 ° C over 1 hour. The reaction mixture was heated to 70 ° C. and kept at this temperature for about 7 hours. After cooling, it was poured into 1 water and extracted with 1 methylene chloride. The organic layer was separated, the Na 2 SO 4 was dried and the solvent was distilled off under a water pump vacuum. The residue was rectified under high vacuum and the fraction boiling at 100-104 ° C. under 3 mbar was collected. 280 g of a clear, colorless oil were obtained.
b)ビス(シクロペンタジエニル)−ビス〔4−
(1′,4′,7′−トリオキサ−n−ウンデク−1−イル
−(2,3,5,6−テトラフルオロフエニル)〕チタノセン
の製造 アルゴン不活性ガス雰囲気下に、51.7gのジエチレン
グリコールモノ−ブチルモノ(2,3,5,6−テトラフルオ
ロ−4−クロロ)−フエニルエーテル(0.15モル)を、
400mlを無水ジエチルエーテルに溶解し、この溶液を−7
5℃まで冷却した。103mlのリチウムブチル−ヘキサン溶
液(1.6ml)を滴下添加後、混合物を15分間−75℃で撹
拌した。b) bis (cyclopentadienyl) -bis [4-
Production of (1 ', 4', 7'-trioxa-n-undec-1-yl- (2,3,5,6-tetrafluorophenyl)] titanocene 51.7 g of diethylene glycol in an argon inert gas atmosphere Mono-butyl mono (2,3,5,6-tetrafluoro-4-chloro) -phenyl ether (0.15 mol)
400 ml was dissolved in anhydrous diethyl ether, and this solution was
Cooled to 5 ° C. After the dropwise addition of 103 ml of lithium butyl-hexane solution (1.6 ml), the mixture was stirred for 15 minutes at -75 ° C.
次に、18.7gのビスシクロペンタジエニルチタニウム
ジクロライド(0.075モル)を、粉末の形態で添加し、
冷却を解除した。混合物を約2時間かけて室温まで温め
るとだいだい赤の不透明溶液になつた。反応混合物を、
1の水中に注入し、総量で600mlの酢酸エチルで何回
にも分けて抽出を行つた。有機相をNa2SO4で乾燥させ、
水流ポンプ真空下に蒸発させた。残留物は58.0gで透明
なだいだい赤の油であつた。この油を移動相として、シ
リカゲル上で2:1ヘキサン−エーテル混合物を使用した
クロマトグラフイーで精製した。溶媒を蒸発させた後に
残る透明粘着性だいだい色の油は、長時間放置後も液状
のまゝであつた。1 H−NMRスペクトルデータ(CDCl3中にて測定) 6.50ppm(5H) 4.32ppm(2H) 3.83,3.70,3.59ppm(6H) 3.47,1.58,1.38,0.92ppm(9H) 250℃において測定したマススペクトルデータ、質量数
(強度) 57(100),72(10),88(18),101(20),145(20),19
3(14),321(2),341(1),357(1),388(1),41
3(1),432(2),796(0.3) 実施例2 チタン化合物として、1当量のビス(メチルシクロペ
ンタジエニル)チタニウムジクロライドを使用し、それ
以外に実施例1と同様の手順に従つて同様の特性を持つ
類似化合物を製造した。ビス(メチルシクロペンタジエ
ニル)−ビス−〔4−(1′,4′,7′−トリオキサ−n
−ウンデカ−1−イル)(2,3,5,6−テトラフルオロフ
エニル)〕−チタノセンが透明なだいだい色の油として
得られ、かなり長期間放置した後も液状のまゝであつ
た。1 H−NMRスペクトルデータ(CDCl3中で測定) 6.52and6.28ppm(4H) 4.35ppm(2H) 3.85,3.69,3.59ppm(6H) 3.47,1.57,1.37,0.92ppm(9H) 1.88ppm(3H) 230℃において測定したマススペクトルデータ、質量数
(強度) 45(50),57(100),72(10),88(20),101(24),145
(20),166(10),193(20),263(2),279(1),281
(1),311(1),369(1),427(1),534(1),550
(1),628(1) 実施例3 ビス(シクロペンタジエニル)−ビス〔4−(1′,
4′,7′,10′−テトラオキサドデシル)−2,3,5,6−テ
トラフルオロフエニル〕−チタニウム トリエチレングリコールモノエチルエーテルを、実施
例1におけるのと同様に、ナトリウムおよびクロロペン
タフルオロベンゼンと反応させた。得られたトリエチレ
ングリコールモノエチルモノ(2,3,5,6−テトラフルオ
ロ−4−クロロフエニル)エーテルは8ミリバールで12
4〜128℃の沸点を持つものである。このエーテルの54.1
gを、実施例1におけると同様に、103mlのリチウムブチ
ル−ヘキサン溶液および18.7gのビス(シクロペンタジ
エニル)チタニウムジクロライドと反応させた。クロマ
トグラフイーで精製後、表題の化合物が透明な粘着性だ
いだい色の油として得られ、かなり長時間放置しても液
状を保つていた。1 H−NMRスペクトルデータ(CDCl3中で測定) 6.49ppm(5H) 4.30ppm(2H) 3.38,3.77−3.57ppm(10H) 3.49,1.22ppm(5H) 250℃において測定したマススペクトルデータ、質量数
(強度) 45(100),72(30),73(54),89(10),117(14),145
(10),161(10),193(30),230(4),237(6),257
(1),273(1),293(1),341(1),390(1),429
(1),502(1),522(1) 実施例4 アクリレート混合物の光硬化について検討した。Next, 18.7 g of biscyclopentadienyltitanium dichloride (0.075 mol) are added in powder form,
The cooling was released. The mixture was allowed to warm to room temperature over about 2 hours, gradually becoming a red, opaque solution. The reaction mixture is
The mixture was poured into 1 of water and extracted in several portions with a total of 600 ml of ethyl acetate. The organic phase was dried over Na 2 SO 4,
Evaporated under a water pump vacuum. The residue weighed 58.0 g and was a clear, red oil. The oil was used as mobile phase and purified by chromatography on silica gel using a 2: 1 hexane-ether mixture. The clear, viscous orange oil that remained after evaporation of the solvent remained liquid after prolonged standing. 1 H-NMR spectrum data (measured in CDCl 3 ) 6.50 ppm (5H) 4.32 ppm (2H) 3.83, 3.70, 3.59 ppm (6H) 3.47, 1.58, 1.38, 0.92 ppm (9H) Mass measured at 250 ° C. Spectral data, mass number (intensity) 57 (100), 72 (10), 88 (18), 101 (20), 145 (20), 19
3 (14), 321 (2), 341 (1), 357 (1), 388 (1), 41
3 (1), 432 (2), 796 (0.3) Example 2 As titanium compound, one equivalent of bis (methylcyclopentadienyl) titanium dichloride was used. Thus, analogous compounds having similar properties were prepared. Bis (methylcyclopentadienyl) -bis- [4- (1 ', 4', 7'-trioxa-n
-Undec-1-yl) (2,3,5,6-tetrafluorophenyl)]-titanocene was obtained as a clear, dark oil which remained liquid after standing for quite some time. 1 H-NMR spectrum data (measured in CDCl 3) 6.52and6.28ppm (4H) 4.35ppm (2H) 3.85,3.69,3.59ppm (6H) 3.47,1.57,1.37,0.92ppm (9H) 1.88ppm (3H) Mass spectrum data measured at 230 ° C, mass number (intensity) 45 (50), 57 (100), 72 (10), 88 (20), 101 (24), 145
(20), 166 (10), 193 (20), 263 (2), 279 (1), 281
(1), 311 (1), 369 (1), 427 (1), 534 (1), 550
(1), 628 (1) Example 3 bis (cyclopentadienyl) -bis [4- (1 ′,
4 ', 7', 10'-Tetraoxadodecyl) -2,3,5,6-tetrafluorophenyl] -titanium triethylene glycol monoethyl ether was converted to sodium and chloropentane as in Example 1. Reacted with fluorobenzene. The resulting triethylene glycol monoethyl mono (2,3,5,6-tetrafluoro-4-chlorophenyl) ether is 12 mbar at 8 mbar.
It has a boiling point of 4 to 128 ° C. 54.1 of this ether
g was reacted as in Example 1 with 103 ml of lithium butyl-hexane solution and 18.7 g of bis (cyclopentadienyl) titanium dichloride. After purification by chromatography, the title compound was obtained as a clear, sticky, dark oil which remained liquid for a considerable period of time. 1 H-NMR spectrum data (measured in CDCl 3 ) 6.49 ppm (5H) 4.30 ppm (2H) 3.38,3.77-3.57 ppm (10H) 3.49,1.22 ppm (5H) Mass spectrum data measured at 250 ° C., mass number (Strength) 45 (100), 72 (30), 73 (54), 89 (10), 117 (14), 145
(10), 161 (10), 193 (30), 230 (4), 237 (6), 257
(1), 273 (1), 293 (1), 341 (1), 390 (1), 429
(1), 502 (1), 522 (1) Example 4 The photocuring of the acrylate mixture was studied.
下記の成分を混合して光硬化性組成物を製造した。 The following components were mixed to produce a photocurable composition.
オリゴウレタン−アクリレート(Actilan AJ20) 50
部 トリエチロールプロパントリアクリレート 20 部 トリプロピレングリコールジアクリレート 15 部 N−ビニルピロリドン 15 部 シリコーン−ベースの流れ調整剤(BYK 300.Byk−Mall
inckrodt,FRG) 0.5部 この組成物の一部を以下の表に示す光重合開始剤また
はその混合物と混合した。開始剤混合物は、式(A) のケタールタイプの液状開始剤中のチタノセン溶液を使
用した。Oligourethane-acrylate (Actilan AJ20) 50
Part Triethylolpropane triacrylate 20 parts Tripropylene glycol diacrylate 15 parts N-vinylpyrrolidone 15 parts Silicone-based flow modifier (BYK 300.Byk-Mall
inckrodt, FRG) 0.5 part A part of this composition was added to a photopolymerization initiator or
Was mixed with the mixture. The initiator mixture has the formula (A)Using a titanocene solution in a ketal-type liquid initiator
Used.
すべての乾燥を赤色光または黄色光下に行つた。 All drying was done under red or yellow light.
開始剤が添加されたサンプルをアルミニウム板(10×
15cm)に100μmの厚さに塗布した。この液体層上に76
μmの厚さのポリエステルフイルムをのせ、21段階の異
なる光学密度(Stouffer wedge)を持つ標準化テストネ
ガをこの上にのせた。さらに第2のポリエステルフイル
ムをこの上にのせ、このようにして得られたラミネート
を金属プレート上に固定した。このサンプルを、30cmの
距離から5kWの金属ハライドランプで露光した。第1テ
ストシリーズにおいては5秒間、第2シリーズにおいて
は10秒間、そして第3シリーズにおいては15秒間露光し
た。露光後、フイルムとマスクを除去し、露光層を15秒
間エタノール浴中で現像し、60℃で5分間乾燥させた。
使用した開始剤系の感度は粘着性なしに画像が形成され
た最終ウエツジステツプを定めることによつて示すこと
ができる。ウエツジステツプの数が多くなればなるほ
ど、その系は感度がそれだけすぐれているということに
なる。ここで2ステツプの増加はほぼ硬化程度が2倍で
あることを意味する。結果は表1に示す通りである。The sample with the initiator added was placed on an aluminum plate (10 ×
15 cm) to a thickness of 100 μm. 76 on this liquid layer
A polyester film having a thickness of μm was placed thereon, and a standardized test negative having 21 different optical densities (Stouffer wedge) was placed thereon. Further, a second polyester film was placed thereon, and the laminate thus obtained was fixed on a metal plate. The sample was exposed with a 5 kW metal halide lamp from a distance of 30 cm. Exposure was for 5 seconds in the first test series, 10 seconds in the second series, and 15 seconds in the third series. After the exposure, the film and the mask were removed, and the exposed layer was developed in an ethanol bath for 15 seconds and dried at 60 ° C. for 5 minutes.
The sensitivity of the initiator system used can be indicated by defining the final wedge step imaged without tack. The greater the number of wet steps, the better the sensitivity of the system. Here, an increase of two steps means that the degree of curing is almost doubled. The results are as shown in Table 1.
実施例5 下記の成分を混合することによつて光硬化性組成物を
製造した。 Example 5 A photocurable composition was produced by mixing the following components.
アセトン中の30%溶液としたスチレン/マレイン酸モ
ノメチル 150.3 部 トリメチロールプロパントリアクリレート 48.3 部 ポリエチレングリコールジアクリレート 6.4 部 クリスタルバイオレツト 0.16部 手順は実施例4におけると同様に行つた。現像は、下
記の組成からなる水性−アルカリ溶液で行つた。Styrene / monomethyl maleate in 30% solution in acetone 150.3 parts Trimethylolpropane triacrylate 48.3 parts Polyethylene glycol diacrylate 6.4 parts Crystal violet 0.16 parts The procedure was as in Example 4. Development was performed with an aqueous-alkaline solution having the following composition.
水 1000 g メタケイ酸ナトリウム 15 g 水酸化カリウム 0.16g ポリエチレングリコール6000 3 g レブリン酸 0.5 g 結果は、表2に示す。Water 1000 g Sodium metasilicate 15 g Potassium hydroxide 0.16 g Polyethylene glycol 6000 3 g Levulinic acid 0.5 g The results are shown in Table 2.
実施例6 実施例4に従って試験用試料を調製した。試料を10秒
間照射した。結果(テストネガの画像が形成されたステ
ップ数)およびテストした化合物は次の表3に示した。 Example 6 A test sample was prepared according to Example 4. The sample was irradiated for 10 seconds. The results (the number of steps at which the test negative image was formed) and the compounds tested are shown in Table 3 below.
実施例7 実施例3の化合物を光開始剤として0.3%含有する試
験用試料を実施例4に従って調製した。20秒照射後のテ
ストネガの画像が形成されたステップ数は5であった。 Example 7 A test sample containing 0.3% of the compound of Example 3 as a photoinitiator was prepared according to Example 4. The number of steps at which a test negative image was formed after irradiation for 20 seconds was 5.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 マンフレッド レンボルト スイス国 4147 エッシュ イム エッ シュヘルト 21 (72)発明者 ブランシシェック ジテーク スイス国 4106 テルヴィル グロスマ ットヴェーク 11 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Manfred Lemboldt Switzerland 4147 Esch im Eschchelt 21 (72) Inventor Branschek Zitek Switzerland 4106 Terville Grossmatteweg 11
Claims (12)
C18のアルキル基で1置換または多置換されたシクロペ
ンタジエニル であり、R2は、金属−炭素結合に対して
の2つのオルト位の少なくとも一方が弗素で置換されて
いる6員の炭素環の芳香族環であって、芳香族環はさら
に置換基を含有してもよく、R3はR2と同一の意味を有
し、R2は少なくとも1個の式−(CzH2zO)0−R9(式
中、zは2−6の数、0は1−20の数でRgはHまたはC1
−C18のアルキル基である)の基を含有し、この基は芳
香族環に直接または式−0−で表わされる架橋基を介し
て結合されていてもよい。] で表わされるチタノセン。(1) Formula (I)[Where the two R1The groups are each independently unsubstituted or C1~
C18Cyclopropyl mono- or polysubstituted with an alkyl group
Ntadienyl And RTwoIs relative to the metal-carbon bond
At least one of the two ortho positions is replaced by fluorine
A six-membered carbocyclic aromatic ring, wherein the aromatic ring is
May contain a substituent, RThreeIs RTwoHas the same meaning as
Then RTwoIs at least one of the formulas-(CzHTwozO)0−R9(formula
Where z is the number of 2-6,0Is a number of 1-20 and Rg is H or C1
−C18Which is an alkyl group).
Directly on the aromatic ring or via a bridging group of formula -0-
May be combined. ] The titanocene represented by these.
ルシクロペンタジエニル である、特許請求の範囲第1
項に記載のチタノセン。[2] R1Is cyclopentadienyl Or meth
Rucyclopentadienyl Claim 1 which is
The titanocene according to the item.
−イルであり、これに対して少なくとも1個の式−(Cz
H2zO)0−R9(式中、zは2−6の数、0は1−20の
数、Rgは水素またはC1−C18のアルキル基である)の基
が直接または式−O−で表わされる架橋基を介して結合
され、さらに1個または2個の同一または異なる置換基
を含有することができるものである、特許請求の範囲第
1項に記載のチタノセン。(3) R 2 and R 3 are 2,6-difluorophen-1
-Yl and at least one of the formulas-(Cz
H 2 zO) 0 -R 9 wherein z is a number of 2-6, 0 is a number of 1-20, and Rg is hydrogen or a C 1 -C 18 alkyl group; 2. The titanocene according to claim 1, which is linked via a bridging group represented by O- and can further contain one or two same or different substituents.
ペンタジエニル またはC1〜C4のアルキル基で置換され
たシクロペンタジエニル であり、R2およびR3が、式 (R5およびR6は各々独立して、HまたはFであり、R7は
式−(CzH2zO)0−R9のポリオキサアルキレン基であっ
て、フェニル環に直接または式−O−で表わされる架橋
基を介して結合されていてもよい。)の基である、特許
請求の範囲第3項に記載のチタノセン。4. In the formula (I), two groups R1But cyclo
Pentadienyl Or C1~ CFourSubstituted with an alkyl group of
Cyclopentadienyl And RTwoAnd RThreeIs the expression(RFiveAnd R6Is each independently H or F;7Is
Formula-(CzHTwozO)0−R9Is a polyoxaalkylene group
To the phenyl ring directly or a bridge represented by the formula -O-
It may be linked via a group. ), The patent
The titanocene according to claim 3.
がエチレンまたは1,2−プリピレンである、特許請求の
範囲第1項に記載のチタノセン。5. The titanocene according to claim 1, wherein the alkylene group in the polyoxaalkylene group is ethylene or 1,2-propylene.
数、oが2−6の数である、特許請求の範囲第1項に記
載のチタノセン。6. The titanocene according to claim 1, wherein R 9 is a C 1 -C 12 alkyl group, z is a number of 2-4, and o is a number of 2-6.
ルシクロペンタジエニル であり、R2およびR3が、式 (式中、R5およびR6は水素または弗素であり、oは2〜
6の数であり、R9はC1〜C12のアルキル基である) の基である、特許請求の範囲第1項に記載のチタノセ
ン。(7) R1But cyclopentadienyl Or meth
Rucyclopentadienyl And RTwoAnd RThreeIs the expression(Where RFiveAnd R6Is hydrogen or fluorine, and o is 2 to
The number 6 and R9Is C1~ C122. The titanose according to claim 1, which is an alkyl group of the formula:
N.
第7項記載のチタノセン。8. The titanocene of claim 7, wherein R 5 and R 6 are fluorine.
C18のアルキル基で1置換または多置換されたシクロペ
ンタジエニル であって、R2は、金属−炭素結合に対し
ての2つのオルト位の少なくとも一方が弗素で置換され
ている6員の炭素環の芳香族環であって、この芳香族環
はさらに置換基を含むものであってもよく、R3はR2と同
一の意味を有し、R2は少なくとも1個の式−(CzH2zO)
0−R9(式中、zは2−6の数、0は1−20の数、Rgは
HまたはC1−C18のアルキルである)の基を含有し、こ
の基は芳香族環に直接または式−0−で表わされる架橋
基を介して結合されていてもよい。] で表わされるチタノセンを製造する当り、式(IV) (式中、R1は上記のとおりであり、Zはハロゲンであっ
て、特に塩素である。)の化合物の1モルとLiR2の2モ
ル(R2は上記のとおりである。)とを反応させ、次に式
(I)の化合物をそれ自体公知の方法で単離することを
特徴とする式(I)のチタノセンの製造法。9. The formula (I)[Where the two R1The groups are each independently unsubstituted or C1~
C18Cyclopropyl mono- or polysubstituted with an alkyl group
Ntadienyl And RTwoIs relative to the metal-carbon bond
At least one of the two ortho positions is replaced by fluorine
A six-membered carbocyclic aromatic ring,
May further include a substituent, and RThreeIs RTwoSame as
Has one meaning, RTwoIs at least one of the formulas-(CzHTwozO)
0−R9(Where z is a number of 2-6,0Is the number of 1-20, Rg is
H or C1−C18Which is an alkyl)
Is directly linked to an aromatic ring or a bridge represented by the formula -0-
It may be linked via a group. In producing the titanocene represented by the formula:(Where R1Is as described above, and Z is halogen.
And especially chlorine. ) And 1 mole of the compoundTwoOf 2
(RTwoIs as described above. ) And then the formula
Isolating the compound of (I) by a method known per se.
A process for producing titanocene of the formula (I), which is characterized in that:
C18のアルキル基で1置換または多置換されたシクロペ
ンタジエニル であり、R2は、金属−炭素結合に対して
の2つのオルト位の少なくとも一方が弗素で置換されて
いる6員の炭素環の芳香族環であって、芳香族環はさら
に置換基を含有してもよく、R3はR2と同一の意味を有
し、R2は少なくとも1個の式−(CzH2zO)0−R9(式
中、zは2−6の数、0は1−20の数でR9はHまたはC1
−C18のアルキル基である)の基を含有し、この基は芳
香族環に直接または式−0−で表わされる架橋基を介し
て結合されていてもよい。] で表わされるチタノセンの少なくとも1種からなること
を特徴とする、少くとも1個のエチレン性不飽和二重結
合を有する重合性非揮発性モノマー、オリゴマーまたは
ポリマー化合物を放射線重合するための開始剤。10. The formula (I)[Where the two R1The groups are each independently unsubstituted or C1~
C18Cyclopropyl mono- or polysubstituted with an alkyl group
Ntadienyl And RTwoIs relative to the metal-carbon bond
At least one of the two ortho positions is replaced by fluorine
A six-membered carbocyclic aromatic ring, wherein the aromatic ring is
May contain a substituent, RThreeIs RTwoHas the same meaning as
Then RTwoIs at least one of the formulas-(CzHTwozO)0−R9(formula
Where z is the number of 2-6,0Is the number of 1-20 and R9Is H or C1
−C18Which is an alkyl group).
Directly on the aromatic ring or via a bridging group of formula -0-
May be combined. ] Consisting of at least one kind of titanocene represented by
At least one ethylenically unsaturated double bond characterized by the following:
Polymerizable non-volatile monomers, oligomers or
Initiator for radiation polymerization of polymer compounds.
含有している、特許請求の範囲第10項に記載の開始剤。11. The initiator according to claim 10, further comprising one or more additional photoinitiators.
ール、4−アロイル−1,3−ジオキソラン、ジアルコキ
シアセトフェノン、α−ヒドロキシまたはα−アミノア
セトフェノンまたはこれらの化合物を含有している特許
請求の範囲第11項に記載の開始剤。12. The method according to claim 1, wherein the photopolymerization initiator contains benzyl ketal, 4-aroyl-1,3-dioxolane, dialkoxyacetophenone, α-hydroxy or α-aminoacetophenone or a compound thereof. Item 12. The initiator according to Item 11.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH310186 | 1986-08-01 | ||
CH3101/86-2 | 1986-08-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6341484A JPS6341484A (en) | 1988-02-22 |
JP2582792B2 true JP2582792B2 (en) | 1997-02-19 |
Family
ID=4248641
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JP62191529A Expired - Lifetime JP2582792B2 (en) | 1986-08-01 | 1987-08-01 | Titanocenes, their preparation and compositions containing them |
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US (3) | US4857654A (en) |
EP (1) | EP0255486B1 (en) |
JP (1) | JP2582792B2 (en) |
KR (1) | KR950008287B1 (en) |
AU (1) | AU599400B2 (en) |
BR (1) | BR8703936A (en) |
CA (1) | CA1332950C (en) |
DE (1) | DE3786205D1 (en) |
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KR910000199B1 (en) * | 1986-04-15 | 1991-01-23 | 시바-가이기 코오포레이숀 | Liquid blend of photoinitiator |
US4857654A (en) * | 1986-08-01 | 1989-08-15 | Ciba-Geigy Corporation | Titanocenes and their use |
US5026625A (en) * | 1987-12-01 | 1991-06-25 | Ciba-Geigy Corporation | Titanocenes, the use thereof, and n-substituted fluoroanilines |
JP2653458B2 (en) * | 1988-03-26 | 1997-09-17 | 旭化成工業株式会社 | Photosensitive resin composition for letterpress printing plates |
US4959284A (en) * | 1988-12-29 | 1990-09-25 | E. I. Du Pont De Nemours And Company | Holographic photopolymer compositions and elements containing a ring-opening monomer |
DE59005996D1 (en) * | 1989-06-01 | 1994-07-14 | Ciba Geigy | Process for the preparation of titanocenes with o, o'-difluoroaryl ligands. |
EP0401165B1 (en) * | 1989-06-01 | 1994-11-30 | Ciba-Geigy Ag | New oxygen-containing titanocenes and their use |
US5068371A (en) * | 1989-06-01 | 1991-11-26 | Ciba-Geigy Corporation | Novel nitrogen-containing titanocenes, and the use thereof |
DE59007720D1 (en) * | 1989-10-27 | 1994-12-22 | Ciba Geigy Ag | Method for tuning the radiation sensitivity of photopolymerizable compositions. |
DE4007428A1 (en) * | 1990-03-09 | 1991-09-12 | Hoechst Ag | Photopolymerisable mixt. sensitive to near UV and visible light |
US5011762A (en) * | 1990-08-14 | 1991-04-30 | Industrial Technology Research Institute | Photosensitive compositions having enhanced photopolymerization rate |
US5514521A (en) * | 1990-08-22 | 1996-05-07 | Brother Kogyo Kabushiki Kaisha | Photocurable composition |
EP0497552B1 (en) * | 1991-01-29 | 1996-05-22 | National Starch and Chemical Investment Holding Corporation | Photopolymerisable compositions |
AU3141193A (en) * | 1991-11-12 | 1993-06-15 | University Of Georgia Research Foundation, Inc., The | Anionic photoinitiation |
US5652280A (en) * | 1991-11-12 | 1997-07-29 | University Of Georgia Research Foundation, Inc. | Anionic photoinitiation |
JP3141517B2 (en) | 1992-05-14 | 2001-03-05 | ブラザー工業株式会社 | Photocurable composition |
JP3426699B2 (en) * | 1994-04-27 | 2003-07-14 | 住友化学工業株式会社 | Process for producing polymer comprising unsaturated carboxylic acid and derivative thereof |
DE4418645C1 (en) | 1994-05-27 | 1995-12-14 | Sun Chemical Corp | Photosensitive mixture and recording material which can be produced therefrom |
DE59507630D1 (en) | 1994-06-13 | 2000-02-24 | Targor Gmbh | Transition metal compounds |
JP3442176B2 (en) | 1995-02-10 | 2003-09-02 | 富士写真フイルム株式会社 | Photopolymerizable composition |
US5837422A (en) * | 1995-07-25 | 1998-11-17 | Mitsubishi Chemical Corporation | Photopolymerizable composition and photosensitive lithographic printing plate employing it |
US5773194A (en) * | 1995-09-08 | 1998-06-30 | Konica Corporation | Light sensitive composition, presensitized lithographic printing plate and image forming method employing the printing plate |
EP0780731B1 (en) | 1995-12-22 | 2002-04-17 | Mitsubishi Chemical Corporation | Photopolymerizable composition for a color filter, color filter and liquid crystal display device |
US6114092A (en) * | 1997-09-29 | 2000-09-05 | Kansai Paint Co., Ltd. | Photosensitive resin compositions for photoresist |
JP4130030B2 (en) | 1999-03-09 | 2008-08-06 | 富士フイルム株式会社 | Photosensitive composition and 1,3-dihydro-1-oxo-2H-indene derivative compound |
DE19961355A1 (en) | 1999-12-17 | 2001-06-21 | S & C Polymer Silicon & Compos | Photoinitiator system with titanocene initiators |
US6936384B2 (en) | 2002-08-01 | 2005-08-30 | Kodak Polychrome Graphics Llc | Infrared-sensitive composition containing a metallocene derivative |
DE10255667B4 (en) | 2002-11-28 | 2006-05-11 | Kodak Polychrome Graphics Gmbh | Radiation-sensitive elements with excellent storage stability |
JP4291638B2 (en) | 2003-07-29 | 2009-07-08 | 富士フイルム株式会社 | Alkali-soluble polymer and planographic printing plate precursor using the same |
US20050153239A1 (en) | 2004-01-09 | 2005-07-14 | Fuji Photo Film Co., Ltd. | Lithographic printing plate precursor and lithographic printing method using the same |
EP1747500A2 (en) | 2004-05-19 | 2007-01-31 | Fuji Photo Film Co. Ltd. | Image recording method |
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US7425406B2 (en) | 2004-07-27 | 2008-09-16 | Fujifilm Corporation | Lithographic printing plate precursor and lithographic printing method |
US20060032390A1 (en) | 2004-07-30 | 2006-02-16 | Fuji Photo Film Co., Ltd. | Lithographic printing plate precursor and lithographic printing method |
EP1630618B1 (en) | 2004-08-24 | 2008-03-19 | FUJIFILM Corporation | Method for producing a lithographic printing plate |
JP2006062188A (en) | 2004-08-26 | 2006-03-09 | Fuji Photo Film Co Ltd | Color image forming material and original plate of lithographic printing plate |
JP2006068963A (en) | 2004-08-31 | 2006-03-16 | Fuji Photo Film Co Ltd | Polymerizable composition, hydrophilic film using this composition and original lithographic printing plate |
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US20060150846A1 (en) | 2004-12-13 | 2006-07-13 | Fuji Photo Film Co. Ltd | Lithographic printing method |
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JP2006335826A (en) | 2005-05-31 | 2006-12-14 | Fujifilm Holdings Corp | Ink composition for inkjet recording and method for manufacturing planographic printing plate using the same |
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EP3577523B1 (en) | 2017-01-31 | 2021-01-13 | Flint Group Germany GmbH | Radiation-curable composition containing low functionalized partially saponified polyvinyl acetate |
US11325368B2 (en) | 2017-03-27 | 2022-05-10 | Flint Group Germany Gmbh | Method for producing pictorial relief structures |
TWI766073B (en) | 2017-07-21 | 2022-06-01 | 台橡股份有限公司 | Composition for preparing a foam, foam and shoe employing the same |
US11822246B2 (en) | 2017-10-10 | 2023-11-21 | Flint Group Germany Gmbh | Relief precursor having low cupping and fluting |
EP3629089A1 (en) | 2018-09-26 | 2020-04-01 | Flint Group Germany GmbH | Method for thermally developing relief precursors |
CN115521344A (en) * | 2021-06-25 | 2022-12-27 | 中国科学院化学研究所 | Metal site substituted metallocene derivative and preparation method and application thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4199420A (en) * | 1978-04-06 | 1980-04-22 | Stauffer Chemical Company | Alkoxymethylbenzophenones as photoinitiators for photopolymerizable compositions and process based thereon |
US4548891A (en) * | 1983-02-11 | 1985-10-22 | Ciba Geigy Corporation | Photopolymerizable compositions containing prepolymers with olefin double bonds and titanium metallocene photoinitiators |
US4590287A (en) * | 1983-02-11 | 1986-05-20 | Ciba-Geigy Corporation | Fluorinated titanocenes and photopolymerizable composition containing same |
US4713401A (en) * | 1984-12-20 | 1987-12-15 | Martin Riediker | Titanocenes and a radiation-polymerizable composition containing these titanocenes |
GB8515475D0 (en) * | 1985-06-19 | 1985-07-24 | Ciba Geigy Ag | Forming images |
US4857654A (en) * | 1986-08-01 | 1989-08-15 | Ciba-Geigy Corporation | Titanocenes and their use |
EP0256981B1 (en) * | 1986-08-01 | 1993-02-17 | Ciba-Geigy Ag | Titanocenes and their use |
US5008302A (en) * | 1987-12-01 | 1991-04-16 | Ciba-Geigy Corporation | Titanocenes, the use thereof, and N-substituted pyrroles |
US5026625A (en) * | 1987-12-01 | 1991-06-25 | Ciba-Geigy Corporation | Titanocenes, the use thereof, and n-substituted fluoroanilines |
-
1987
- 1987-07-24 US US07/077,261 patent/US4857654A/en not_active Expired - Lifetime
- 1987-07-24 AU AU76169/87A patent/AU599400B2/en not_active Ceased
- 1987-07-27 EP EP87810430A patent/EP0255486B1/en not_active Expired - Lifetime
- 1987-07-27 DE DE8787810430T patent/DE3786205D1/en not_active Expired - Lifetime
- 1987-07-30 CA CA000543475A patent/CA1332950C/en not_active Expired - Fee Related
- 1987-07-31 SU SU874203074A patent/SU1597105A3/en active
- 1987-07-31 BR BR8703936A patent/BR8703936A/en unknown
- 1987-07-31 ZA ZA875671A patent/ZA875671B/en unknown
- 1987-08-01 KR KR1019870008512A patent/KR950008287B1/en not_active IP Right Cessation
- 1987-08-01 JP JP62191529A patent/JP2582792B2/en not_active Expired - Lifetime
-
1989
- 1989-06-05 US US07/361,194 patent/US4970136A/en not_active Expired - Lifetime
-
1990
- 1990-08-21 US US07/570,497 patent/US5034307A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
US5034307A (en) | 1991-07-23 |
ZA875671B (en) | 1988-02-01 |
CA1332950C (en) | 1994-11-08 |
KR950008287B1 (en) | 1995-07-27 |
US4970136A (en) | 1990-11-13 |
KR880002882A (en) | 1988-05-12 |
AU599400B2 (en) | 1990-07-19 |
SU1597105A3 (en) | 1990-09-30 |
BR8703936A (en) | 1988-04-05 |
US4857654A (en) | 1989-08-15 |
AU7616987A (en) | 1988-02-04 |
DE3786205D1 (en) | 1993-07-22 |
EP0255486A2 (en) | 1988-02-03 |
EP0255486B1 (en) | 1993-06-16 |
JPS6341484A (en) | 1988-02-22 |
EP0255486A3 (en) | 1990-06-06 |
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